Miticidal fluorinated carbonates

ABSTRACT

Fluorinated carbonates are described which are useful as miticides. These carbonates often possess herbicidal, insecticidal, and/or fungicidal properties. Examples of the fluorinated carbonates at 2&#39;&#39;, 4&#39;&#39;-dinitro-6&#39;&#39;-sec-butylphenyl2,2,2-trifluoroethyl carbonate; 2&#39;&#39;,4&#39;&#39;-dinitro-6&#39;&#39;-sec-butylphenyl2,2,3,3-tetrafluoropropyl carbonate and 2&#39;&#39;,4&#39;&#39;-dinitro-6&#39;&#39;cyclohexylphenyl 2,2,3,3-tetrafluoropropyl carbonate.

United States Patent [1 1 Hardies et al.

[451 Dec. 3, 1974 1 MITICIDAL FLUORINATED CARBONATES [75] Inventors: Donald E. l-lardies, Wadsworth; Jay 1 K. Rinehart, Akron, both of Ohio [73] Assignee: PPG Industries, Inc., Pittsburgh, Pa.

[22] Filed: Oct. 24, 1972 [21] Appl. No.: 299,968

Related US. Application Data [62] Division of Ser. No. 76,275, Sept. 28, 1970, Pat. No

Ncwnllis ct al. 1 260/445 Hardies ct a1 .1 260/463 Primary ExaminerAlbert T. Meyers Assistant Examiner-Leonard Schenkman Attorney, Agent, or FirmGeorge D. Morris 5 7 ABSTRACT Fluorinated carbonates are described which are useful as miticides. These carbonates often possess herbicidal, insecticidal, and/or fungicidal properties. Examples of the fluorinated carbonates at 2', 4-dinitro-6- sec-butylphenyl-Z,2,2-trifluoroethyl carbonate; 2',4- dinitro-6'-sec-butylphenyl-2,2,3,3-tetrafluoropropyl carbonate and 2,4'-dinitro-6'-cyclohexylphenyl 2,2,3,3-tetrafluoropropyl carbonate 7 Claims, N0 Drawings MITICIDAL FLUORINATED CARBONATES CROSS-REFERENCE TO RELATED APPLICATION This application is a division of our earlier filed, copending application Ser. No. 76,275, filed Sept. 28, 1970, now US. Pat. No. 3,742,010, issued June 26, 1973.

In accordance with this invention, there are provided carbonates which are effective as miticides and which also often possess herbicidal, insecticidal and/or fungicidal properties.

Carbonates here contemplated may be represented by the formula wherein x is 1, 2 or 3;

k is -2, 0 or 2;

m is an integer ranging from 1 to when k is 2;

m is an integer ranging from 2 to 15 when k is 0 or n is an integer ranging from 1 to (2m-l-k-l and R is hydrogen, lower alkyl, halo lower alkyl, lower alkenyl, halo lower alkenyl, lower alkylthio, halo lower alkylthio, lower alkenylthio, halo lower alkenylthio, lower cycloalkyl or halo lower cycloalkyl.

The value for k depends upon the type of bonding in the C,,,I-I ,,F radical. In general, for aliphatic straight or branched chain radicals where d is the number of double bonds in the radical, and

t is the number of triple bonds in the radical.

Thus, for aliphatic, straight, or branched chain radicals when k 2 the radical is a fluoroalkyl,-when k 0 the radical is a fluoroalkenyl, and when k 2 the radical is a fluoroalkynyl. Most often, k 2.

R typically contains up to 8 carbon atoms. It ordinarily is a straight or branched lower alkyl group or halo lower alkyl group having 1 to 8 carbon atoms. Often such groups having from 1 to 4 carbon atoms are used. The secondary butyl group is preferred. When R is lower cycloalkyl or halo lower cycloalkyl, it ordinarily contains from 3 to 8 carbon atoms. Most often such groups have from 5 to 8 carbon atoms. ,Of these cyclic groups, cyclohexyl is preferred.

When R is halo substituted, the halo substituents are usually fluoro, chloro, bromo and/or iodo. Chloro and- 4. The valueof n is also frequently an even integer ranging from 4 to 20.

NO (II) wherein m is an integer ranging from 1 to 15, more usually ranging from 2 to 11 or 3 to ll; n is an integer ranging from 1 to (2m+1); and R is lower alkyl or halo lower alkyl ordinarily containing from 1 to 8 carbon atoms or cycloalkyl or halo cycloalkyl ordinarily containing from 3 to 8 carbon atoms. When R is lower alkyl or halo lower alkyl, it usually contains from 1 to 4 carbon atoms. When R is cycloalkyl or halo cycloalkyl it usually contains from 5 to 8 carbon atoms. R is preferably secondary butyl or cyclohexyl. An important class falling within the generic invention is represented by the formula:

OCOCI-l (CF CF H (III) No wherein or halo lower alkyl, it usually contains from 1 to 4 carbon atoms. When R is lower cycloalkyl or halo lower cycloalkyl, it usually contains from 5 to 8 carbon atoms. R is preferably secondary butyl or cyclohexyl. 1 The nitro groups and R may be located in any position on the ring. Often the ring is substituted by two nitro groups which are usually in the 2',4-positions while R is usually located in the 6-position. This results in the subclass:

u OCOCt-I (CF c 2 H 3 wherein i is an integer ranging from 1 to 7, more often ranging from 1 to 5; and R is lower alkyl or halo lower alkyl ordinarily containing from 1 to 8 carbon atoms or lower cycloalkyl or halo lower cycloalkyl ordinarily containing from 3 to 8 carbon atoms. When R is lower alkyl or halo lower alkyl, it usually contains from 1 to 4 carbon atoms. When R is lower cycloalkyl or halo lower cycloalkyl, it usually contains from 5 to 8 carbon atoms. R is preferably secondary butyl or cyclohexyl. Of especial importance are the compounds 2',4-dinitro-6'-secbutylphenyl 2,2,3,3-tetrafluoropropyl carbonate:

0, ll OCOCH CF CF H 2 2 2 (v) CH CH SZH N and 2,4'-dinitro-6-cyclohexylphenyl 2,2,3,3-tetrafluoropropyl carbonate:

' Y I OCOCH CF CF H I (VI) Another important class falling within the generic in-- vention is represented by the formula l OCOCH (CF2 F (VII) wherein x is l, 2 or 3; g is an integer ordinarily ranging from 1 to 14 and,

most often, from l to ll or 4 to 11; and R is lower alkyl or halo lower alkyl oridinarily containing from 1 to 8 carbon atoms or lower cycloalkyl or halo lower cycloalkyl containing from 3 to 8 carbon atoms. When R is lower alkyl or halo lower alkyl, it usually contains from 1 to 4 carbon atoms. When R is lower cycloalkyl or halo lower cycloalkyl, it usually contains from to 8 carbon atoms. R is preferably secondary butyl or cyclohexyl. The nitro groups and R may be located in any position on the ring. Often the ring is substituted by two nitro groups which are usually in the 2',4'-positions while R is usually located in the 6-position. This results in the 4 subclass:

a OCOCH (CF' F 2 2 9 (VIII) wherein g is an integer ordinarily ranging from 1 to 14 and,

most often, from 1 to 11 or 4 to ll; and R is lower alkyl or halo lower alkyl ordinarily containing from 1 to 8 carbon atoms or lower cycloalkyl or halo lower cycloalkyl ordinarily containing from 3 to 8 carbon atoms. When R is lower alkyl or halo lower alkyl, it usually contains from 1 to 4 carbon atoms. When R is lower cycloalkyl or halo lower cycloalkyl, it usually contains from 6 to 8 carbon atoms. R is preferably secondary butyl or cyclohexyl. Of importance is the compound 2,4-dinitro-6'-secbutylphenyl 2,2,2-trifluoroethyl carbonate:

u ococn cr CH3CH2C\ZH 6 N0 lIX) Still another important class falling within the generic invention is represented by the formula:

ll OCO(CF2)J-F wherein x is l, 2 or 3; 1 j is an integer ranging from 1 to l5, more often rangingfrom2tollor3to1l;and R is lower alkyl or halo lower alkyl ordinarily containing from 1 to 8 carbon atoms or lower cycloalkyl orhalo lower cycloalkyl ordinarily containing from 3 to 8 carbon atoms. When R is lower alkyl or halo lower alkyl, it usually contains from 1 to 4 carbon atoms. When R is lower cycloalkyl or halo lower cycloalkyl, it usually contains from 5 to 8 carbon atoms. R is preferably secondary butyl or cyclohexyl. The nitro groups and R may be located in any position on the ring. Often the ring is substituted by two nitro groups which are usually in the 2',4'-positions while R is usually located in the 6-position. This results in the subclass:

N02 7 (XI) wherein 2',4',5-trinitrophenyl 2,2,2-trifluoroethyl carbonate 2, 4,5'-trinitro-6-sec-butylphenyl trifluoromethyl carbonate- 2' ,4 ,5 '-trinitro-6 -isopropylphenyl hexafluorohexyl carbonate 2,4,5'-trinitro-6-methylphenyl 2-fluoroethyl carbonate 2',4,6'-trinitro-3'-ethylphenyl 2-fluoropropyl carbonate 2',4',6'-trinitro-3'-methylphenyl 1H, 1H, 9H-

hexadecafluorononyl carbonate 2' ,4 ,6 -trinitro-3 '-methylphenyl perfluoroheptyl EXAMPLE I Phosgene (74 g.) was condensed into anhydrous diethyl ether (200 ml.) contained in a one liter, threenecked flask at ice bath temperature. The compound 2,2,2-trifluoroethanol (25.0 g.) in diethyl ether (75 ml.) was added in a stream to the reaction mixture. Anhydrous pyridine (22 g.) in diethyl ether (25 ml.) was added dropwise to the stirred reaction mixture while maintaining a temperature of 4C. to 12C. The dropwise addition of the pyridine was accomplished over a 30-minute period. There was an instantaneous precipitation of pyridine hydrochloride upon addition of the first drop of pyridine. The reaction mixture was stirred for 3 hours while warming to room temperature. The excess phosgene was removed from the reaction mixture under a fine stream of argon. The precipitated pyridine hydrochloride was then removed by filtration and the filtrate distilled under a nitrogen bleed to remove the solvent. Distillation of the residue under a pressure of 165 Torr gave the product (17.8 g.) as a colorless liquid. The boiling point of the product was 40 C. at 165 Torr. The structure 2,2,2-trifluoroethyl chloroformate was confirmed by nuclear magnetic resonance (NMR) spectroscopy.

The sodium salt of 2,4-dinitro-6-sec-butyl phenol was prepared by combining 2,4-dinitro-6-sec-butyl phenol (7.9 g.), sodium hydroxide (2.0 g.) and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were added. The compound 2,2,2-trifluoroethyi chloroformate (4.9 g.) was added dropwise to the, vigorously stirred reaction mixture over a 30-minute period while maintaining the temperature in the range of 24C.27C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined withe the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10 percent aqueous sodium hydroxide, one portion (100 ml.( of 10 percent hydrochloric acid and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 5.4 g. of crude oil which crystallized upon standing. The product was recrystallized from diethyl ether--normal pentane to give 4.2 g. of yellow crystals having a melting point of 91C.93C. The infrared spectrum showed the carbonate ester absorption at 1,782 cm This product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 1.

Table 1 Analysis of 2',4-dinitro-6'-sec-butylphenyl 2,2,2-trifluoroethyl carbonate Calculated for C, H F;N,O 42.63 3.58 7.65 First Analysis 43.32 3.27 8.04 Second Analysis 43.28 3.26 8.11

The product may be depicted as having the structural formula:

0 Oi ZOCH CF cn cn lzn no 2 EXAMPLE ii Phosgene (74 g.) was condensed into anhydrous diethyl ether (200 ml.) contained in a one liter, threenecked flask at ice bath temperature. The compound 2,2,3,3-tetrafluoro-l-propanol (33.0 g.) in diethyl ether (75 ml.) was added in a stream to the reaction mixture. Anhydrous pyridine (22 g.) in diethyl ether (25 ml.) was added dropwise to the stirred reaction mixture while maintaining a temperature of 2'C. to 8C. The dropwise addition of the pyridine was accomplished over a 20-minute period. There was an instantaneous precipitation of pyridine hydrochloride upon addition of the first drop of pyridine. The reaction mixture was stirred for 3 hours while warming to room temperature. The excess phosgene was removed from the reaction mixture under a time stream of argon. The precipitated pyridine hydrochloride was then removed by filtration and the filtrate distilled under a nitrogen bleed to remove the solvent. Distillation of the residue under a pressure of 50 Torr gave the product (33.1 g.) as a colorless liquid. The boiling point of the product was 48C.-49C. at 50 Torr. The structure 2,2,3,3-tetrafluoropropyl chloroformate was confirmed by NMR spectroscopy.

The sodium salt of 2,4-dinitro-6-sec-butyl phenol was prepared by combining 2,4-dinitro-6-sec-butyl phenol (9.6 g.), sodium hydroxide (2.4 g.) and water (150 ml.). Unstabilized methylene chloride ml.) and triethylamine (1 ml.) were then added. The compound 2,2,3,3-tetrafluoropropyl chloroformate (7.8 g.) was added dropwise to the vigorously stirred reaction mixture over a 15-minute period while maintaining the temperature in the range of 25C.29C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of percent aqueous sodium hydroxide, one portion (100 ml.) of 10 percent hydrochloric acid and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 12.0 g. of crude oil which crystallized upon cooling in ice. The product was recrystallized'from diethyl ether-- -norma1 pentane to give 6.7 g. of yellow crystals having a melting point of 45C.-48C. The infrared spectrum showed the carbonate ester absorption at 1,784 cm. This product was analyzed for carbon, hydrogen and nitrogen. The results expressed in percent by weight are shown in Table 2.

Table 2' Analysis of 2',4'-dinitro-6'-sec-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate Calculated for C H IZN O 42.22 3.54 7.04 First Analysis 41.96 3.18 6 96 Second Analysis 42.1 1 3.29

The product may be depicted as having the structural formula:

The sodium salt of 2,4-dinitro-6-cyclohexy1phenol was prepared by combining 2,4-dinitro 6-cyclohexyl phenol (5.3 g.), sodium hydroxide (1.2 g.) and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound 2,2,3,3-tetrafluoropropy1 chlorofonnate (3.9 g.) was added dropwise to the vigorously stirred reaction mixture over a 10-minute period while maintaining the temperature in the range of 24C.26C. The reaction mixture was stirred for an additional minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10 percent aqueous sodium hydroxide, one portion (100 ml.) of 10 percent hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 5.0 g. of crude oil which crystallized upon cooling in ice. The product was recrystallized from diethyl ether- -normal pentane to give 3.5 g. of pale yellow crystals having a melting point of 89C.92C. The infrared spectrum showed the carbonate ester absorption at 1,780 cm". This product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 3.

Table 3 Analysis of 2,4'-dinitro-6-cyclohexylphenyl 2,2,3,3-tetrafluoropropyl carbonate Calculated for c,,H,,F,N,o, 45.29 3.80 6.60 First Analysis 44.99 4.03 6.45 Second Analysis 45.23 3.88

The product may be depicted as having the structura formjula:

EXAMPLE IV temperature in the range of 22C.25C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml. The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10 percent aqueous sodium hydroxide, one portion (100 ml.) of 10 percent hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 5.4 g. of oil which would not crystallize. The infrared spectrum showed the carbonate ester absorption at 1,783 cm. Purity was established as about percent by NMR spectroscopy.

The product may be depicted as having the structural formula:

EXAMPLE V equal volume of diethyl ether was added in a stream to i the mixture. Anhydrous pyridine (43.5 g.) dissolved in an equal volume of diethyl ether was added dropwise to the stirred reaction mixture while maintaining a temperature of C. to C. The dropwise addition of the pyridine was accomplished over a period of about one hour. The reaction mixture was stirred an additional one hour at 0C. to 10C., then for 2 hours while gradually warming up to room temperature. The excess phosgene was removed from the reaction mixture under a fine stream of nitrogen. The precipitated pyridine hydrochloride was then removed by filtration and washed with diethyl ether. The diethyl ether wash was squeezed out of the paper into the filtrate. The filtrate was dried with sodium sulfate and diethyl ether solvent was removed by a one-plate distillation at atmospheric pressure. One-plate distillation of the residue under reduced pressure gave product 180.5 g.) having an assay of 94.9 percent. The boiling-point of the product, 1H, 1H, 7H-dodecafluoroheptyl chloroformate, was 420C. at 1.1 Torr. The sodium salt of 2,4-dinitro-6- sec-butyl phenol was prepared by combining 2,4-dinitro-6-sec-butyl phenol (7.4 g.), sodium hydroxide (1.8 g.), and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were .then added. The compound 1H, 1H, 7l-l-dodecafluoroheptyl chloroformate (13.0 g.) was added dropwise to the vigorously stirred reaction mixture over a 45-minute period while maintaining the temperature in the range of 22C.25C. The reaction mixture was stirred for an additional minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml. The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10 percent aqueous sodium hydroxide, one portion (100 ml.) of 10 percent hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 15.5 g. of oil which would not immediately crystallize. The infrared spectrum showed the carbonate ester absorption at 1,780 cm". Purity was established to be about 94 percent by NMR spectroscopy. The product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 4.

Table 4 Analysis of 2',4'-dinitro-6'-sec-butyl 1H,1 H.7H-dodecafluoroheptyl carbonate Calculated for C H F N,O 36.13 2.36 4.68 First Analysis 33.84 2.31 6.58 Second Analysis 34.19 2.14 6.58

Table 5 Analysis of 2,4'-dinitro-6-sec-butylphenyl l H, l H,7H-dodecafluoroheptyl carbonate rim Analysis Second Analysis The product may be depicted as having the structural formula:

EXAMPLE Vl Phosgene (89.0 g.) was condensed into anhydrous diethyl ether (200 ml.) contained in a one liter, fournecked, round-bottom flask equipped with a dropping funnel, a solid carbon dioxide condenser, a polytetrafluoroethylene blade paddle stirrer, a thermometer, and a phosgene inlet. The compound 1H, 1H, 11H- eicosafluoro-l-undecanol (159.6 g.) dissolved in an equal volume of diethyl ether was added in a stream to the mixture. Anhydrous pyridine (26.1 g.) dissolved in an equal volume of diethyl ether was added dropwise to the stirred reaction mixture while maintaining a tem perature of 0C. 10C. The dropwise addition of the pyridine was accomplished over a period of about one hour. The reaction mixture was stirred an additional hour at 0C. 10C., then for 2 hours while gradually warming up to room temperature. The excess phosgene was removed from the reaction mixture under a fine stream of nitrogen. The precipitated pyridine hydrochloride was then removed by filtration and washed with diethyl ether. The diethyl ether wash was squeezed out of the paper into the filtrate. The filtrate was dried with sodium sulfate and diethyl ether solvent was removed by a one-plate distillation at atmospheric pres sure. The solid residue was recrystallized from nhexane, yielding crystals (89.7 g. having an assay of 78.4 percent and a melting point of 57.5C.58.0C. The product was 1H, 1H, llH-eicosafluoroundecyl chloroformate.

The sodium salt of 2,4-dinitro-6-sec-butyl phenol was prepared by combining 2,4-dinitro-6-sec-butyl phenol (4.8 g.), sodium hydroxide (1.2 g.), and water (150 ml.). Unstabilized methylene chloride ml.) and triethylamine (1 ml.) were then added. The compound 1H, 1H, lll-l-eicosafluoroundecyl chloroformate 13.1 g.) was added dropwise to the vigorously stirred reaction mixture over a 35-minute period while maintaining the temperature in the range of 24C .26C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride 100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10 percent aqueous sodium hydroxide, one portion (100 ml.) of 10 percent hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 14.1 g. of crude oil which crystallized. The product was recrystallized from diethyl ether-normal pentane to give 6.5 g. of crystals having a melting point of 100.5C.-103C. The infrared spectrum showed the carbonate ester absorption at 1,784 cm". This product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 6.

Table 6 Analysis of 2',4-dinitro-6'-sec-butylphenyl 1H,1H,1ll-l-eicosafluoroundecyl carbonate Calculated for C H F N,O-, 33.1 1.77 3.51 First Analysis 32.56 2.94 365 Second Analysis 32.61 1.90 Third Analysis 32.41 1.97

The product may be depicted as having the structural formula:

Phosgene (158.3 g.) was condensed into anhydrous diethyl ether (200 ml.) contained in a one liter, fournecked, round-bottom flask equipped with a dropping funnel, a solid carbon dioxide condenser, a polytetrafluoroethylene blade paddle stirrer, a thermometer, and a phosgene inlet. The compound 1- (trifluoromethyl-Z,2,2-trifluoroethanol (117.6 g.) dissolved in an equal volume of diethyl ether was added in a stream to the mixture. Anhydrous pyridine (69.6 g.) dissolved in an equal volume of diethyl ether was added dropwise to the stirred reaction mixture while maintaining a temperature of C. to C. The dropwise addition of the pyridine was accomplished over a period of about one hour. The reaction mixture was stirred an additional hour at 0C. to 10C., then for 2 hours while gradually warming up to room temperature. The excess phosgene was removed from the reaction mixture. The precipitated pyridine hydrochloride was then removed by filtration and washed with diethyl ether. The diethyl ether wash was squeezed out of the paper into the filtrate. The filtrate was dried with sodium sulfate anddiethyl ether solvent was removed by a one-plate distillation at atmospheric pressure. Tenplate distillation of the residue at atmospheric pressure gave product 46.4 g.) having an assay of 93 percent. The product was trifluoroethyl chloroformate.

The sodium salt of 2,4-dinitro-6-sec-butyl phenol was prepared by combining 2,4-dinitro-6-sec-butyl phenol (8.4 g.), sodium hydroxide (2.1 g.), and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound 1-trifluoromethyl)-2,2,2-trifluoroethyl chloroformate (8.3 g.) was added dropwise to the vigorously stirred reaction mixture over a 20-minute .period while maintaining the temperature in the range of 25C.27C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions 100 ml. each) of 10 percent aqueous sodium hydroxide, one portion 199 ml.) of 10 percent hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 12.4 g. of crude oil which crystallized. The product-was recrystallized from diethyl ether-normal pentane to give 8.8 g. of crystals having a melting point of 62.5C.-64.5C. The infrared spectrum showed the carbonate ester absorption at 1,795 cm. The product was analyzed for carbon, hydrogen, and nitrogen. The results expressed in per cent by weight are shown in Table 7.

Table 7 Analysis of 2',4'-dinitro-6-sec-butylphenyl The product may be depicted as having the structural formula:

O CF OCOCHCF CH CH C'IH N0 CI-l EXAMPLE VIII The sodium salt of 2,4-dinitro phenol was prepared by combining 2,4-dinitro phenol (7.3 g.), sodium hydroxide (2.4 g.), and water ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound 2,2,3,3tetrafluoropropyl chloroformate (8.5 g.) was added dropwise to the vigorously stirred reaction mixture over a 20- minute period while maintaining the temperature in the range of 24.5C.27.5C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10 percent aqueous sodium hydroxide, one portion (100 ml.) of 10 percent hydrochloric acid and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 11.7 g. of oil which would not crystallize. The infrared spectrum showed the carbonate ester absorption at 1,785 cm. Purity was established to be about 92 percent by NMR spectroscopy.

The product may be depicted as having the structural (96.1 g.) dissolved in an equal volume of diethyl ether formula: was added in a stream to the mixture. Anhydrous pyrio dine (130.5 g.) dissolved in an equal volume of diethyl u ether was added dropwise to the stirred reaction mixococ 1 C15 H ture while maintaining a temperature of 0C. to C.

2 2 2 The dropwise addition of the pyridine was accomplished over a period of about 1 hour. The reaction mixture was stirred an additional hour at 0C. to 10C.,

then for 2 hours while gradually warming up to room NO l0 temperature. The excess phosgene was removed from the reaction mixture. The precipitated pyridine hydrochloride was then removed by filtration and washed EXAMPLE [X with diethyl ether. The diethyl ether wash was squeezed The Sodium Salt 0f 2,6-dinitrO P enol wa prepared out of the paper into the filtrate. The filtrate was dried by Combining 2,6-dinhr0 phenol g-), Sodi hywith sodium sulfate and diethyl ether solvent was re dIOXide g), and Water Unstabililed moved by a one-plate distillation at atmospheric presmethylene Chloride and ri y n sure. One-plate distillation of the residue under rewere then added. The compound 2,2,3,3etetrafluorodu ed pressure gave product (93.7 g.) having an assay propy ChlOfOfOfmate g-) Was added dTOPWiSe of 85.4 per cent. The boiling point of the product, 2- the vigorously stirred reaction mixture over a 20 fl thyl hl formate, was 690C. at 100 Torr. minute period while maintaining the temperature in the Th di lt f 2,4-dinitr0-6-sec-butyl phenol was range Of -5C-- -5C- The reaction mixture was prepared by combining 2,4-dinitro-6-sec-butyl phenol stirred for an additional 15 minutes. The two layers (12 di h d xid (3,0 and water (150 were separated an he q e y r w Washed with ml. Unstabilized methylene chloride (100 ml.) and methy n Chloride The resulting layers 25 triethylamine (1 ml.) were then added. The compound were separated and the organic layer was combined 2-fluoroethyl chloroformate (6.9 g.) was added dropwith the Organic layer from the first Separation The wise to the vigorously stirred reaction mixture over a combined Organic ye were Washed with two P 15-minute period while maintaining the temperature in liens each) 0f 10 P aqueous Sodium ythe range of 27C.-29C. The reaction mixture was dfOXide, one Pomoh of 10 Percent y 30 stirred for an additional 15 minutes. The two layers chloric acid, and dried over sodium sulfate. The solvent were separated d th aqueous layer was washed with was removed on a rotary evaporator to g 111'! gof A methylene chloride (100 ml.). The resulting layers Crude Oil which crystaniled- The Product was 'y were separated and the organic layer was combined lized from diethyl ether--normal pentane to give 4.0 g. ith th organic layer from th first separation. The of crystals having a melting point of 685C. 7l.5C. combined organic layers were h d i h two The infrared spectrum showed the carbonate ester abtions (100 l, h) f 10 percent aqueous sodium hysorption at 1,790 T product was analyzed for droxide, one portion (100 m1.) of 10 percent hydro- C hydrogen, and g The results expressed chloric acid and dried over sodium sulfate. The solvent in P y weight are shown in Table was removed on a rotary evaporator to give 3.3 g. of

Table 8 40 crude oil which crystallized. The product was recrystallized from diethyl ether-normal pentaneto give 1.9 g.

Analysis of zztdinitmphenyl of crystals having a melting point of 7.7.5C.80.5C. 2,2,3,3-tetraluoropropyl calrlbonate N The infrared spectrum showed the carbonate ester absorption at 1772 cm". The product was analyzed for calculated for carbon, hydrogen and nitrogen. The results expressed m t 4 1 35-10 8J9 in percent by weight are shown in Table 9.

Found 35.1 1 2.01 8.22

I Table 9 The product may be depicted as having the structural Analysis of 2',4-dinitro-6'sec-butylphenyl formula: Z-fluoroethyl carbonate 7 c H N 0 Calculated for c,,H,,FN,o, 47.28 4.58 8.48 First Analysis 47.84 4.91 8.63 OCOCHZCFZCFZH Second Analysis 47.60 a 4.84

The product may be depicted as having the structural formula:

O EXAMPLE X 11 Phosgene (296.7 g.) was condensed into anhydrous OCoCH2CH2F diethyl ether (200 m1.) contained in a one liter, fourv CH CH CH NO necked, round-bottom flask equipped with a dropping 3 2 funnel, a solid carbon dioxide condenser, a polytetra- 7 CH3 fluoroethylene blade paddle stirrer, a thermometer, and a phosgene inlet. The compound Z-fluoroethanol EXAMPLE XI The sodium salt of 2,4-dinitro-6-tert-butyl phenol was prepared by combining 2,4-dinitro-6-tert-butyl phenol (7.2 g.), sodium hydroxide (1.8 g.), and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound 2,2,3,3-tetrafluoropropyl chloroformate (6.4 g.) was added dropwise to the vigorously stirred reaction mixture over a 15-minute period while maintaining the temperature in the range of 23.5C.56.5C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of percent aqueous sodium hydroxide, one portion (100 ml.) of 10 percent hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 8.7 g. of crude oil which crystallized. The product was recrystallized from diethyl ether--normal pentane to give 3.5 g. of crystals having a melting point of 88.5C.-9l .5C. The infrared spectrum showed the carbonate ester absorption at 1,778 cm. The product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 10.

Table 10 Analysis of 2',4'-dinitro-6'-tert butylphenyl 2,2,3,3-tetrafluoropropyl carbonate The product may be depicted as having the structural formula:

EXAMPLE XII The sodium salt of 2,4-dinitro-6-cyclohexyl phenol was prepared by combining 2,4-dinitro-6-cyclohexyl phenol (12.0 g.), sodium hydroxide (2.7 g.), and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound 2-fluoroethyl chloroformate (6.2 g.) was added dropwise to the vigorously stirred reaction mixture over a 25-minute period while maintaining the temperature in the range of 25C.27C. The reaction mixture was stirred for an additional minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two porlyzed for carbon, hydrogen and nitrogen. The results expressed in percent by weight are shown in Table 1 1.

Table 1 1 Analysis of 2',4'-dinitro-6-cyclohexylphenyl 2-fluoroethyl carbonate C H N Calculated for C H FN O 50.56 4.81 7.86 Found 49.8 4.50 7.77

The product may be depicted as having the structural formula:

i OCOCH CH F EXAMPLE XIII The sodium salt of 2,4-dinitro-6-cyclohexyl phenol was prepared by combining 2,4-dinitro-6-cyclohexyl phenol (9.3 g.), sodium hydroxide (2.1 g.), and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound l-(trifluoromethyl)-2,2,2-trifluoroethyl chloroformate (8.8 g.) was added dropwise to the vigorously stirred reaction mixture over a 28-minute period while maintaining the temperature in the range of 25.5C.28C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml. The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10 percent aqueous sodium hydroxide, one portion 23 Table 12 Analysis of 2',4-dinitro-6'-cyclohexylphenyl l-( trifluoromethyl )-2,2,2-trifluoroethyl carbonate C H N Calculated for C 16 HFBNZO'I Found OCOCHCF EXAMPLE XIV The sodium salt of 2,4-dinitro-6-cyclohexyl phenol was prepared by combining 2,4-dinitro-6-cyclohexyl phenol (7.0 g.), sodium hydroxide (1.6 g.), and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound 1H,1H,7H-dodecafluoroheptyl chloroformate (11.0 g.) was added dropwise to the vigorously stirred reaction mixture over a 30-minute period while maintaining the temperature in the range of 24.5C.26.5C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions 100 ml. each) of 10 percent aqueous sodium hydroxide, one portion (100 ml.) of 10 percent hydrochloric acid and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 14.4 g. of crude oil which crystallized. The product was recrystallized from 'diethyl ether--normal pentane to yield 6.5 g. of crystals having a melting point range of 685C. to 72C. The infrared spectrum showed the carbonate ester absorption at 1,780 cm. The product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 13.

Table 13 Analysis of 2',4-clinitro-6-cyclohexylphenyl 1H,11-1,7H-dodecafluoroheptyl carbonate The product may be depicted as having the structural formula:

0 ll ococa (cF cF 3H EXAMPLE xv The sodium salt of 2,4-dinitro-6-cyclohexyl phenol was prepared by combining 2,4-dinitro6-cyclohexyl phenol (5.3 g.), sodium hydroxide (1.2 g.) and water (150 ml.). Unstabilized methylene chloride (ml) and triethylamine (1 ml.) were then added. The compound lH,1H,lll-l-eicosafluoroundecyl chloroformate (13.0 g.) was added dropwise to the vigorously stirred reaction mixture over a 25-minute period while maintaining the temperature in the range of 24C.25C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with twoportions (100 ml. each) of 10 percent aqueous sodium hydroxide, one portion 100 ml.) of 10 percent hydrochloric acid and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 9.6 g. of crude oil which crystallized. The product was recrystallized from diethyl ether--normal pentane to yield 5.8 g. of crystals having a melting point range of l 19C. to 123C. The infrared spectrum showed the carbonate ester absorption at 1780 cm. The product was analyzed for carbon, hydrogen and nitrogen. The results expressed in percent by weight are shown in Table 14.

Table 14 Analysis of 2,4'-dinitro-6'-cyc1ohexylphenyl 1 H, l H, l 1H-eicosafluoroundecyl carbonate The product may be depicted as having the structural formula:

0 ll OCOCH (CF CF H Many of the fluorinated alcohols used to prepare the precursor chloroformates and many of the substituted phenols are known to the art. In those instances where the compounds having the desired substitutions are not available, they may be prepared by any of the methods well known in chemistry. in the case of compounds falling within the scope of formula ([11,) a particularly advantageous method is available for preparing the precursor alcohol which consists in reating methanol with one or more equivalents of tetrafluoroethylene in the presence of a free radical initiator. The over-all equation for the reaction is:

HOCl-l, nCF =CF HOCH,( CF,CF ),,H More specific details of this reaction may be found in US. Pat. Nos. 2,959,611 and 2,559,628. The 1,1- dihydroperfluoroalkyl alcohols and their preparation are described in US Pat. No. 2,666,767. The reaction between fluoro alcohols and phosgene to form chloroformates is described in US. Pat. No. 2,959,611. The preparation of perfluoroalkyl chloroformates from perfluoroalkyl hypochlorites is described by Young et al., Perfluoroalkyl Chloroformates and Chlorosulfates, Tetrahedron Letters, No. 9 (1969) Pergamon Press, pp. 723-726. The fluorinated alkenyl chloroformates and fluorinated alkynyl chloroformates may be prepared by methods analogous to those for preparing the fiuorinated alkyl chloroformates.

In general, the carbonates of this invention may be used to kill or retard development of mites.

In one embodiment the carbonate is applied directly to the mites. In another embodiment the carbonate is applied to regions where mites are likely to be found in order to kill the mites present or to preclude mite populations from becoming established.

Usually formulations containing from about to about 2,000 parts per million by weight (ppm) of the carbonate compound are applied. Typical formulations contain from about 10 to about 1,000 ppm. Often formulations containing from about 10 to about 100 ppm are used.

The type of formulation used may vary. Solutions and suspensions of the carbonate are effective. The usual method of applying solutions or suspensions is to drench the area of application. Sprays, showers, mists and dips may be used for this purpose. When some of ing about 10 percent acetone, 0.020 percent Span 85 and 0.0050 percent. Tween 80. The amount of test compound dissolved in the stock acetone emulsion is such that when diluted with deionized water the concentrated test solution has the highest concentration (usually 1,000 ppm) of test compound used in the tests. Other solutions are prepared by diluting the concentrated test solution with a mixture of deionized water and stock acetone emulsion, which mixture contains about 10 percent acetone, 0.020 percent Span 85, and 0.0050 per cent Tween 80. Thus, all test solutions always contain about 10 percent acetone, 0.020 percent Span 85, and 0.0050 percent Tween 80, irrespective of the concentration of test compound. Compounds giving an unsatisfactory formulation as an acetone emulsion are formulated as wettable powders and diluted the more active carbonates are used, particularly at I higher concentrations, a complete drenching is not necessary. Mists are often used where a drench is not desired. I

The carbonate formulations of the invention may also be applied in the form of a powder or dust. These powders or dusts may contain diluents such as, for example, aluminum silicate, bentonite, calcium carbonate, calcium silicate, diatomaceous silica, hydrated lime, pulverized limestone, montmorillonite, pulverized phosphate rock, silica, talc, or vermiculite.

The concentration of the carbonate compound in the formulation and the total amount applied will vary depending upon the particular carbonate being employed and the particular mite being confronted. Other factors such as season of the year, environmental conditions, and stage of mite development all have their effect.

The following specific embodiments illustrate, by way of example, the basic principles of the present invention:

EXAMPLE XVI Potted horticultural bean plants (Phaseolus vulgaris, L.) at growth stage when primarily leaves are approximately 1 inch long are infested with two-spotted spider mites (Tetranychus urticae) 24 hours prior to treatment, insuring establishment of adults and deposition of eggs at the time of treatment.

When possible, the test compounds are formulated as follows: A stock acetone emulsion is prepared having the following composition by weight: 99.75 percent acetone, 0.20 percent sorbitan trioleate (Span 85), and 0.05 percent sorbitan monooleate polyoxyalkylene derivative (Tween 80). Test compound is dissolved in a portion of the stock acetone emulsion. Deionized water is added to yield a concentrated test solution containwith water and wetting agent before application.

Infested host plants are dipped into agitated solutions of the test compound, allowed to air dry, provided with a subterranean water source, and held for observation. Three test plants are used for each unit of treatment.

Initially mortality is determined 48 to 72 hours after treatment by removing and observing one leaf from each plant. Final observations of mortality, ovicidal action, and residual toxicity to emerging nymphs are made 7 days after treatment by removal and observation of the second primary leaf. The observed results are reported in terms of Percent Mortality. Table 15 reports observed results where the test compound is 2', 4-dinitro-6-secbutylphenyl 2,2,2-trifluoroethyl car bonate.

butylphenyl 2,2,3,3-tetrafluoropropyl carbonate. Table 16 reports the observed results of this test.

Table 16 Miticidal Effectiveness of 2, 4'-Dinitro-6'-butylphenyl 2,2,3,3-Tetrafluoropropyl Carbonate Against Two-Spotted Spider Mite (Tetranychus urticae) Concentration Percent Mortality ppm Initial Ovicidal Residual 1,000 100 No Young 500 100 100 N0 Young 250 100 I00 No Young 100 100 10 EXAMPLE xvm The procedure of Example XVI is repeated except 2',4'-dinitro-6'- that the test compound is cyclohexylphenyl 2,2,3,3-tetrafluoropropyl carbonate. 5

Miticidal Effectiveness of 2', 4'-Dinitro-6'-cyclohexylphenyl 2,2,3,3-Tetrafluoropropyl Carbonate Against Two-Spotted Spider Mite (Tetranychus urticae) Concentration Percent Mortality ppm Initial Ovicidal Residual l ,000 88 Trace 90 50 24 0 25 5 0 0 l0 8 0 0 Table Miticidal Effectiveness of 2, 4'-Dinitro-6'-sec-butylphenyl l-(Trifluoromethyl)-2,2,2-trifluoroethyl Carbonate Against Two-Spotted Spider Mite (Telranyckus uru'cae) Concentration Percent Mortality ppm Initial Ovicidal 1,000 100 100 500 I00 I00 250 I00 90 I00 100 60 50 100 S5 I00 Trace 10 50 0 5 l0 0 EXAMPLE XXII.

The procedure of Example XVI is repeated except that the test compound is 2, 4-dinitrophenyl 2O 2,2,3,3-tetrafluoropropyl carbonate. Table 21 reports EXAMPLE XIX the observed results of this test.

The procedure of Example XVI is repeated except T bl 21 that the test compound of 2 4-dinitro 6'- y p y 2,2,3,3-teIraflu0r0Pr0P/1 Carbonate 25 Miticidal Effectiveness of 2', 4'-Din itrophenyl 2,2,33- Table 18 reports the observed results of this test. Tmuorqpwwlcfltbonaw Agams T Spider Mite (Tetranychus umvae) Table 18 Concentration Percent Mortality ppm Initial Ovicidal Miticidal Effectiveness of 2', 4'-Dinitro-6'-meth vl- Y phenyl 2,2,3,3-Tetrafluoropropyl Carbonate Against 1,000 We 80 Two-Spotted Spider Mile (Tetranychus urticae) Trgce Concentration Percent Mortality loo 4 0 ppm Initial Ovicidal Residual 50 16 0 0 EXAMPLE XXIII g g 0 g The procedure of ExampleXVI is repeated except that the test compound 18 2 6 -drmtrophenyl 2,2,3,3-tetrafluoropropyl carbonate. Table 22 reports P 40 the observed results of this test.

EXAM LE XX Table 22. The procedure of Example XVI 1S repeated except that thetest compound is 2', 4'- initro-6'-sec- Miticidal Effectiveness of 2', 6'-Dinitrophenyl 2.2,3,3- butylphenyllI-I, lI-I, llH-eicosafluoroundecyl carbon- TetfafluorqvwvylaCarbonate AsamstTwo-spofied Spider Mite (Tetranychus umcae) ate. Table 19 reports the observed results of this test.

- Concentration Percent Mortality ppm Initial Ovicidal Table 19 1,000 26 0 Miticidal Effectiveness of 2, 4'-Dinitro-6-sec-butylphenyl 1H,] HJ lH-Eicosafluoroundecyl Carbonate Against Two-Spotted Spider Mite (Tetranychus um'cae) EXAMPLE XXIV Concmlration Pmem Mortality The procedure of Example XVI is repeated except ppm that the test compound is 2', 4-dinitro-6'-sec- 1,000 97 0 butylphenyl 2-fluoroethyl carbonate. Table 23 reports 500 87 25 the observed results of this test. 250 25 Trace :00 19 0 Table 23 p Miticidal Effectiveness of 2', 4-Dinitro-6'-sec-butylphenyl Z-Fluoroethyl Carbonate Against Two-Spotted EXAMPLE XXI Spider Mite (Terranychus urticae) The procedure of Example XVI is repeated except Concentration I Percent Mortality that the test compound is 2', 4-dinitr0-6'-secppm butylphenyl l-(trifluoromethyl)-2,2,2-trifluoroethyl 1,000 100 carbonate. Table 20 reports the observed results of this 328 Y test.

Table 23-Continued Miticidal Effectiveness of 2', 4-Dinitro-6-sec-butylphenyl 2-Fluoroethyl Carbonate Against Two-Spotted Spider Mite (Tetranychus urticae) Concentration Percent Mortality ppm Initial Ovicidal 50 85 100 25 30 20 I 8 Trace EXAMPLE XXV The procedure of Example XVI is repeated except that the test compound is 2, 4'-dinitr0-6'-tertbutylphenyl 2,2,3,3-tetrafluoropropyl carbonate. Table 24 reports the observed results of this test.

Table 24 Miticidal Effectiveness of 2, 4'-Dinitro-6'-tert-butylphenyl 2,2,3,3-Tetrafluoropropyl Carbonate Against Two-Spotted Spider Mite (Tetmnychus urticae) Concentration Percent Mortality ppm Initial Ovicidal l ,000 100 100 500 100 80 250 95 Trace I00 66 0 Table 25 Miticidal Effectiveness of 2, 4-Dinitro-6-sec-butylphenyl lH,1H,7I-{-Dodecafluoroheptyl Carbonate Against Two-Spotted Spider Mite (Tetranychu: urticae) Concentration Percent Mortality ppm Initial Ovicidal I ,000 I00 45 500 100 70 250 I00 30 I O0 53 Trace Many of the carbonates of the present invention possess properties which make them useful as phytocides, as for example, herbicides. Weeds may be killed by applying to the soil in the vicinity of the weeds a phytocidal amount of the carbonate. Weeds may also be killed by bringing a phytocidal amount of the carbonate and the weeds into mutual contact, as for example, by applying the carbamate directly to the weeds. In another embodiment the carbonate is applied to the soil where weeds are likely to be found in order to preclude weeds from becoming established.

The formulations used as phytocides are similar in all material respects to those described above for miticidal purposes. The concentration of the carbonate compound in the formulation and the total amount applied will vary depending upon the particular carbonate being employed and the particular weed being confronted. Other factors such as season of the year, environmental conditions and stage of weed development all have their effect. Exemplary application rates are from about 0.1 to about 100 pounds per acre. Usually the rate will range from about 0.1 to about 20 pounds per acre. Rates of from about 0.5 to about 10 pounds per acre are most often used.

In Examples XVII through LI the following procedure was used: For pre-emergence testing, appropriate weed species are seeded in individual disposable threeinch square containers containing about 2 inches of soil. After spraying directly on the seeded soil surface, a small amount of sand, usually about A; to V; inch i depth, is applied to cover the seeds.

For post-emergence testing, appropriate weed species are seeded by growth-time requirement schedules in individual disposable 3 inch square containers containing about 2 inches of soil, watered as required, and maintained under greenhouse conditions. When all weeds have reached suitable growth development, gen erally first true leaf stage, plants appropriate to pertaining test requirements are selected for uniformity of growth and development. One container of each weed,

, averaging up to 50 plants per individual container, is

then placed on a carrying tray for treatment.

When possible, the test compounds are formulated in a sovlent mixture of percent acetone, 8 percent methanol, and 2 percent dimethylformamide by volume. Insoluble compounds are formulated as wettable powders and diluted with water and wetting agent before application.

Each carrying tray of pre-emergence and/or post emergence containers, placed on a conveyor belt having a linear speed of 1.5 miles per hour, trips a micro.- switch which, in turn, activates a solenoid valve and releases the compound under test. The compound under test is discharged as sprays at a rate of 50 gallons per acre. Containers for both pre-emergence and postemergence testing are then removed to the greenhouse and held for observation.

Pre-emergence and post-emergence treatments are observed daily for interim response, final observations usually being made 14 days after treatment. Any treatments inducing significant response are held beyond the 14-day observation period until such responses can be confirmed. Each result is reported as an Injury Rating which is represented as follows: 0 no visible effect; 1, 2, 3 slight injury, plant usually recovered with little or no reduction in top growth; 4, 5, or 6 moderate injury, plants usually recovered but with reduced top growth; 7, 8, or 9 severe injury, plants usually did not recover, l0 all plants killed. Deviations from the above procedure, if any, are reported with the data.

EXAMPLE-XXVI] Test Compound: 2',4-Dinitro-6'-sec-butylphenyl 2,2,2-

trifluoroethyl carbonate Pre-Emergence Observations made 21 days after application Post-Emergence Observations made 9 days after application Pre- Post- Test Plant r 10 lb./A I0 lbJA Yellow Nutsedge (Cyperu: esculentus I...) 0 0 Wild Oats (Avena fatua L.)

' 3,852,464 31 ExAnrreiizvn 'caminued Test Compound: 2',4'-Dinitro-6 sec-butylphenyl 2,2,2-

trifluoroethyl carbonate Pre-Emergence Observations made 21 days after application Post-Emergence Observations made 9 days after application Pre- Post- Test Plant Emergence Emergence l0 lbJA l0 lb./A

Jirnsonweed (Datum stmmanium L.) l0 l0 Velvetleaf (Abuu'lan theophrasti Medic.) 8 l0 Johnsongrass (Sorghum halepense Pers.) l 3 Lambsquarter (Chenapodium album L.) 10 Mustard (Brarsica kaber L. C. Wheeler Var. pinnanfida L. C. Wheeler) l0 l0 Yellow Foxtail (Setaria glqugq lieauv.) Q 0 Barnyardgrass (Echinochloa crusgalli Beauv.) l 2 Crabgrass (Digitaria sanguinalis'Scop.) 2 3 Buckwheat (Palygonum convolvulus L.) 9 10- Morning Glory (mixture of Ipomoea purpurea Roth and lmpomoea Itederacea .lacq.) 8 10 Red Kidney Bean (Phaseolus vulgaris L.) 3

Untreated Controls Normal Normal EXAMPLE xxvtn Test Compound: 2',4'-Dinitro-6'-sec-butylphenyl 2,2,2-trifluoroethyl carbonate Observations made 16 days after application Pre-Emergence Test Plant 5 lb/A 2.5 lb/A 1.25 lb/A Yellow Nutsedge (Cyperus esculen'tus L.) 0 0 0 Wild Oats (Avena fatua L.) l 0 0 Jirnsonweed (Datum stramonium L.) 9 8 8 Velvetleat' Mbutilon theophrasti I Medic.) 9 8 0 .lohnsongrass (Sorghum halepenre Pers.) O 0 0 Lambsquarter (Chenopodium album L.) l0 l0 l0 Mustard (Brassica kaber L. C. Wheeler 7 Var. pinnarifida L. C. Wheeler) l0 l0 9 Yellow Foxtail (Setarin glauca Beauv.) 2 0 0 Barnyardgrass (Echinochloa crusgalli Beauv.) 3 0 0 Crabgrass (Digigaria sanguinnlis Scop.) 2 0 0 Buckwheat (Polygonum convolvulus L.) 9 9 9 Morning Glory (mixture of Ipomaea purpurea Roth and Ipomoea hederacea Jacq.) 2 4 l Untreated Controls Normal Normal Normal EXAMPLE XXIX Test Compound: 2',4'-Dinitro-tS'-see-butylphenyl 2.2,2-trifluoroethyl carbonate Observations made 21 days after application Pre-Emergenge 'Test Plant 5 lb/A 2.5 lb/A L25 lb/A Yellow Nutsedge (Cyperus esculenlus L.) O O 0 Wild Oats (Avena fatua L.) 0 O 0 .limsonweed (Datum .rtmmonium L.) l0 l0 l0 Velvetleaf (Abun'lon theophrasn' Medic.) l0 l0 0 Johnsongrass (Sorghum halepense Pers.) 0 0 0 Lambsquarter [Cheiwpodium album L.) l0 l0 5 Mustard (Brmsica lazbez L. C. Wheeler Var. pinnatzfidd L. C. Wheeler) 10 l0 10 Yellow Foxtail (Semn'a glauca Beauv.) 2 0 0 Barnyardgrass (Echinochloa crurgalli Beauv.) 3" 0 0 Crabgrass (Dt'gitaria sanguinalis Scop.) v 2 0 0 Buckwheat (Polygonum convolvulus L.) 1O l0 9 Morning Glory (mixture of lpomoea purpurea Roth and lpomoea hederacea Jacq.) 2 4 2 Untreated Controls Normal Normal Normal EXAMPLE XXX Test Compound: 2',4-Dinitro-6'-sec-butylphenyl 2,2,2-trifluoroethyl carbonate Observations made 13 days after application Post-emer nc Test Plant 5 lb/A 2.5 lb/A 1.25 lb/A Yellow Nutsedge (Cyperus esculentus L.) 2 0 0 Wild Oats (Avena fatua L.) 3 2 l .limsonweed (Datum stramonium L.) l0 l0 l0 Velvetleaf (Abutilon theophrasti Medic.) l0 l0 l0 Johnsongrass (Sorghum halepense Pers.) O 0 0 Mustard (Brassica kaber L. C. Wheeler Var. pinnatifida L. C. Wheeler) 10 l0 10 Yellow Foxtail (Seran'a glauca Beauv.) O 0 0 Bamyardgrass (Echinochloa crusgalli Beauv.) 0 0 0 Grabgrass (Digimria sanguinalis Scop.) 0 O 0 Buckwheat (Polygonum convolvulus L.) l0 l0 10 Morning Glory (mixture of lpomoea purpurea Roth and Ipomoea hederacea Jacq.) l0 l0 7 Red Kidney Bean (Phaseolus vulgaris L.)

Primary Leaf Stage 0 0 0 Trifoliate Leaf Stage 1 l l Untreated Controls Normal Normal Nonnal EXAMPLE XXXl Test Compound: 2',4'-Dinitro-6-sec-butylphenyl 2,2,3 ,3-tetrafluoropropyl carbonate Pro-Emergence Observations made 21 days after application. Post-Emergence Observations made 9 days after application.

Pre- Post- Test Plant Emergence Emergence l0 lb./A 10 lb/A Yellow Nutsedge (Cyperus esculentus L.) 0 1 Wild Oats (Avena fatua L.) 6 l0 Jimsonweed (Datura stramonium L.) l0 l0 Velvetleaf (Abutilon theophrasti Medic.) 10 10 Johnsongrass (Sorghum halepense Pers.) 0 2 Lambsquarter (Chenopodium album L.) 10 Mustard (Brassica kaber L. C. Wheeler Var. pinnarifida L. C. Wheeler) l0 10 Yellow Foxtail (Seraria gluuca Beauv.) 0 2 Barnyardgrass (Echinochloa crusgalli Beauv.) l 3 Crabgrass (Digiraria sanguinalis Scop.) 7 2 Buckwheat (Polygonum convolvulus L.) 8 10 Morning Glory (mixture of lpomoea purpurea Roth and lpomoea hederacea Jacq.) 8 l0 Red Kidney. Bean (Phasealus vulgaris L.) 0 Untreated Controls Normal Normal EXAMPLE XXXII Test Compound: 2',4-Dinitrol-6-sec-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate Observations made 16 days after application Pre-Emgrgence Test Plant 5 lb/A 2.5 lb/A L25 lb/A Yellow Nutsedge (Cyperus esculenlus L.) Wild Oats (Averuz fatua L.) Jimsonweed (Datum .rtrnmonium L.) Velvetleaf (Aburilon theaphrasti Medic.) Johnsongrass (Sorghum halepense Pers.) Lambsquarter (Chenopodium album L.) Mustard (Bnmim kaber L. C. Wheeler Var. tinnalxfida L. C. Wheeler) l0 l0 l0 Yellow Foxtail (Semria glauca Beauv.) Barnyardgrass (Echinochloa crusgalli Beauv.) Crabgrass (Digitaria sanguinalis Sco Buckwheat (Polygonum convalvulus L.) Morning Glory (mixture of lpamoea purpurea Roth and lpomoea hederacea Jaeq.) 5 l l Untreated Controls 4 Normal Non-rial Normal COO OOC OOQ OOO OQO WOO ecu N N Mustard (Bmssica kaber L. C. Wheeler EXAMPLE XXXIII Test Compound: 2',4'-Dinitro-6 sec-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate Observations made 21 days after application l e- Ems nmc e Test Plant 5 lb/A 2.4 lb/A 1.25 lb/A Yellow Nutsedge (Cyperus esculemus L.) 0 0 0 Wild Oats (Avemz fatua L.) 0 0 0 Jimsonweed (Datum stramonium L.) 10 9 9 Velvetleaf (Abutilon theophrasti I Johnsongrass {Sorghum halegense Pers.) 0 0 0 Lambsquarter (Chenopodium album L.) l0 l0 5 Mustard (Brassica kaber L. C. Wheeler Var. pinnatzfida L. C. Wheeler) 10 l0 10 Yellow Foxtail (Setaria glauca Beauv.) 0 O 0 Barnyardgrass (Echinovhloa crusgalli I Beauv.) 2 0 0 Crabgrass (Digiraria sanguinalis Scop.) 2 0 O Buckwheat (Palygonum cunvolvulus L.) 10 8 8 Morning Glory (mixture of Ipomoea purpurea Roth and Ipomoea hederacea I Jacq.) 4 2 L) V. Untreated Controls Normal Normal Normal EXAMPLE XXXIV Test Compound: 2,4-Dinitro-6'-sec-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate Observations made 13 days after application Post-Emer ence Test Plant 5 lb/A 2.5 lb/A 1.25 lb/A Yellow Nutsedge (Cyperus esculentus L.) 2 0 0 Wild Oats (Avena fatua L.) 8 6 4 Jirnsonweed (Datura stramonium L.) l0 10 1O Velvetleaf (Abutilon Iheophrasti Medic.) l0 l0 l0 Johnsongrass (Sorghum halepense Pers.) 3 l 0 Mustard (Brassica kaber L. C. Wheeler 1 Var. pirmatifida L. C. Wheeler) l0 l0 10 Yellow Foxtail (Setaria glauca Beauv.) l 0 0 Barnyardgrass (Echinochloa crusgalli Beauv.) 8 4 2 Crabgrass (Digimria sanguinalis Scop.) l 0 0 Buckwheat (Polygonum convolvulus L.) l0 l0 10 Morning Glory (mixture of lpomoea purpurea Roth and lpomoea hederacea Jacq.) l0 10 9 Red Kidney Bean (Phasealus vuIgarisL.)

Primary Leaf Stage l 0 0 Trifoliate Leaf Stage 0 0 0 Untreated Controls Normal Normal Normal EXAMPLE XXXV Test Compound: 2,4-Dinitro-6'-eyclohexylphenyl 2,2,3,3-tetrachloropropyl carbonate Pre-Emergence Observations made 13 days after application Post-Emergence Observations made 14 days after application A I Pre- Post- Test Plant r r 10 lbJA l0 lbJA Yellow Nutsedge (Cyperus esculenms' L.) Wild Oats (Avuqa futon L.)

Jimsonweed (Damn: srmmonium L.) Velvetleaf (Abulilon lheophmsti Medic.) .lohnsongrass (Sorghum Ilakpense Pets.) Pigweed (Amaranth: rermflexus L.)

Var. pinnatifida L. C. Wheeler) Yellow Foxtail (Setan'a glauca Beauv.)

Barnyardgmss (EChiIIOd'llOG crusgalli Beauv.)

Crabgras (Digitarin sanguinali: Scop.)

Buckwheat (Polygonum convolvulu: L.)

Morning Glory (mixture of lpomoea purpurea Roth and Ipomoea hederacea Jacq.)

Red Kidney Bean (Phaseolus vulgaris L.)

Primary Leaf Stage Trifoliate Leaf Stage Untreated Controls Normal 3,852,464 37 3s EXAMPLE XXXVI Test Compound: 2,4-Dinitro-6'-methylphenyl 2.2.3.3-tetrafluoropropyl carbonate Pre-Emergence Observations made 13 days after application Post-Emergence Observations made 14 days after application Pre- Post- Test Plant r n Emer n e 10 lb./A l lbJA Yellow Nutsedge (Cyperus esculemus L.) 0 0 Wild Oats (Avena fatua L.) l 9 Jimsonweed (Datura stramom'um L.) 0 l0 Velvetleaf (Abutilon theaphrasti Medic.) 0 l0 Johnsongrass (Sorghum halepense Pets.) 2 0 Pigweed (Amaranthus retmflexus L.) 9 Mustard (Emssica kaber L. C. Wheeler Var. pinnatifida L. C. Wheeler) 8 Yellow Foxtail (Setarla glauca Beauv.) 2 0 Bamyardgrass (Echinochlua crusgalli Beauv.) 0 7 Crabgrass (Digitaria sanguinnlis Soup.) 3 8 Buckwheat (Polyganum convolvulu: L.) 4 10 Morning Glory (mixture of Ipamaea purpurea Roth and lpomoea hederacea .lacq.) 6 8 Red Kidney Bean (Phaseolus vulgar-is L.)

Primary Leaf Stage l Trifoliate Leaf Stage 0 Untreated Controls Normal Normal EXAMPLE XXXVI] Continued Test Compound: 2,4'-Dinitro-6'-methylphenyl 2,2 ,3 vI'l-tetrafluoropropyl carbonate Observations. made 21 days after application- EXAMPLE XXXVII Test Compound: 2,4'-Dinitro-6'-methylphenyl 2,2,3,3-tetrafluoropropyl carbonate Observations made 21 days after application Pre- Pre- Test Plant Emer- Test Plant Emergence gence l0 lb./A I0 |b./A

Yellow wild gg 35,;figj'fff 2 Yellow Foxtail (Seturia glauca Beauv.) 2 Jimsonweed (Datum stramonium L.) 0 g g g 'f i Beau) 0 Velvetleaf (Abutl'lon theophrasri Medic.) o 'g P- 2 Johnsongrass (Sorghum halep nse Pers.) 0 a 3 5 g q f fy 3 Plgweed (Amaranthus retroflexus L.) 9 40 and I g de me I? Pomoell P i Roth Mustard (Brassica kaber L. C. Wheeler Umr e acql') 2 Var. pinnatifida L. C. Wheeler) 9 ea 6 0mm 8 Noflflall EXAMPLE XXXVIII Test Compound: 2',4-Dinitro-6-sec-butylphenyl 1H, 1 H, l ll-l-eicosafluoroundecyl carbonate Observations made 13 days after application (left column) Observations made 23 days after application (right column) 1' Test Plant 10 lbJA l0 Ila-IA" Yellow Nutsedge (Cyperus esculenrus L.) 0 0 Wild Oats (Avena falua L.) 0 0 Jimsonweed (Datum srramonium L.) 8 8 Velvetleaf (Abutilon theophraxn' Medic.) 6 4 Johnsongrass (Sorghum halepense Pers.) 0 0 Pigweed (Amaranthus relroflexus L.) 10 8 Mustard (g assjca jgglzgr L. C. Wheeler Var. pinnanfida L. C. Wheeler) 10 10 Yellow Foxtail (Selarl'a glauca Beauv.) 9* 9* Barnyardgrass (Echinochloa crusgalli Beauv.) 3 2 Crabgrass (Dl'gitaria sanguinalis Scop.) 3 0 Buckwheat (Polygonum convolvulus L.) 3 0 Morning Glory (mixture of Ipomoea purpurea Roth and lpomoea hederacea Jacq.) v 2 l v Untreated Controls Normal Normal *Possible bird damage 

1. A METHOD OF KILLING MITES WHICH COMPRISES APPLYING TO THE MITES OR THEIR PLANT HABITAL A MITICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA:
 2. The method of claim 1 wherein the value of k is 2 and R is selected from the group consisting of lower alkyl containing from 1 to 8 carbon atoms and lower cycloalkyl containing from 3 to 8 carbon atoms.
 3. The method of claim 2 wherein a. the value of x is 2; b. the nitro groups are located in the 2'',4''-positions; and c. R is located in the 6''-position.
 4. The method of claim 3 wherein R is secondary butyl or cyclohexyl.
 5. The method of claim 4 wherein the compound is 2'',4''-dinitro-6''-sec-butylphenyl 1-(trifluoromethyl)-2,2,2-trifluoroethyl carbonate.
 6. The method of claim 4 wherein the compound is 2'',4''-dinitro-6''-sec-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate.
 7. The method of claim 4 wherein the compound is 2'',4''-dinitro-6''-sec-butylphenyl 2-fluoroethyl carbonate. 